D-Arabinose (3). A mixture of 2 (200 g, 0.43 mol from oxidation of D-glucose 1), Ba(OAc)2 (20 g,0.08 mol) and Fe2(SO4)3 (10 g, 0.025 mol) was stirred in water (2 L) until a precipitate appeared. The suspension was filtered and the brown solution was treated with 30% H2O2 (129 mL) at 35 ℃. A second portion of 30%H2O2 (120 mL) was added and all was warmed to 40 ℃. Filtration on Norite, evaporation (in vacuum), addition ofMeOH, filtration and crystallization gave 55–60 g of 3 (50%), mp 162–164 ℃, [a]D =103°.【J. Am. Chem. Soc., 1950, 72, 4546】
To a stirred mixture of 1.716 g 3-deoxy-l-hexonolactone, 34 mL water, 442 mg calciumhydroxide, 272 mg barium acetate monohydrate, and 170 mg hydrous ferrous sulfate wasadded 2 mL 30% H2O2, and an additional 2 mL 30% H2O2 was added after 45 min of stirring. Then the solution was kept at room temperature for 2 h with occasional stirring,and then treated with decolorizing carbon and fifiltered. The fifiltrate was passed successivelythrough columns of Amberlite IR-120 (H+) (40 mL) and Amberlite IR-4 (OH−) (40 mL).Concentration in vacuo gave 430 mg of a yellow syrup, in a yield of 30%.【J. Org. Chem., 1968, 33, 1816】
A solution of 20.86 g barium acetate monohydrate (0.076 mol) in 60 mL water and asolution of 10.2 g ferric sulfate (0.0255 mol) in 60 mL water (equimolecular quantities) arepoured into 2 L distilled water in a 4-L glass beaker. Calcium gluconate dihydrate (200 g,0.43 mol) was then added, and the solution was heated to boil with stirring. The solution wasthen removed from the flflame, allowed to settle, and fifiltered on a Buchner funnel precoatedwith fifiltercel. To the clear amber-colored fifiltrate,1Lwater was added, and the solution wascooled to 35◦C, then 120 mL 30% H2O2 was added. Within a few minutes, an evolution ofgas began, and the temperature rose spontaneously to ∼ 55◦C. The reaction was completein about 30 min, as indicated by the sudden appearance of a dark purple color. After themixture cooled to 40◦C, an additional 120 mL 30% H2O2 was added, whereupon a newreaction took place very similarly. The dark turbid solution was then fifiltered through carbonon a Buchner funnel and concentrated to 250 mL under vacuum. To this solution was added1500 mL methanol with shaking, and the granular precipitate was fifiltered on a Buchnerfunnel precoated with carbon and washed with 300 mL methanol. To the clear fifiltrate wasadded 900 mL ether with shaking. After 5 min of settling, the new granular precipitatewas fifiltered on a carbon-coated Buchner funnel. The fifiltrate was concentrated to a syrupunder vacuum. When it had become so stiff as barely to flflow, it was taken up in ∼100 mLwarm methanol and poured out into an Erlenmeyer flflask; another 25 mL methanol wasused for rinsing. Crystallization took place readily without seeding. After a few hours in therefrigerator, the sugar was fifiltered, washed with MeOH and dried. The yield was 55–65 gor ∼ 42.6–50% of the theoretical amount. It was recrystallized by being dissolved in twothirds its weight of water and fifilter with carbon rapidly while hot; fifive volumes of methanolwas added. Sharp prisms of d-arabinose separated in a yield of 80% of the crude substanceused. The product was dried at 60◦C under vacuum for 2 h, m.p. 155.5–156.5◦C.【J. Am. Chem. Soc., 1934, 56, 1632】相关文献1、Fenton O., Proc. Chem. Soc., 1893, 9, 113.2、Ruff, O., Ber., 1898, 31, 1573.3、Stapley, J. A. and BeMiller, J. N., Carbohydr. Res., 2007, 342, 407.4、Hourdin, G.; Germain, A.; Moreau, C. and Fajula, F., J. Catal., 2002, 209, 217.5、Marcq, O.; Barbe, J.-M.; Trichet, A. and Guilard, R., Carbohydr. Res., 2001, 333, 233.6、Fajula F., Cat. Lett., 2000, 69, 241.7、 Neira A., J. Chil. Chem. Soc., 2007, 52, 1314.
参考资料一、Comprehensive Organic Name Reactions and Reagents, by Zerong Wang，P2446-2449.二、Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 411.
